Azo compounds



Patented May 2, 1944 AZO COIVIPOUNDS James G. McNally and Joseph B.Dickey, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester,N. Y., a corporation of New Jersey No Drawing. Application January 8,1942,

' Serial No. 426,056

3 Claims.

This invention relates to the new azo compounds having the formula:

represents a member selected from the group con-' sisting of aB-hydroxyethyl group, a ,B-hydroxypropyl group, a 'y-hydroxypropylgroup, a 8,

dihydroxypropyl group, a p-methoxyethyl group, and a fi-ethoxyethylgroup and X represents a member selected from the group consisting ofhydrogen and a methyl group and to textile materials colored therewith.

The azo compounds of our invention constitute valuable dyes for thecoloration of textile materials such as organic derivatives ofcellulose, wool, silk, nylon and Vinyon and wool-like fibers derivedfrom protein-like materials, such as casein wool. They are particularlyof value for the coloration of cellulose acetate. Lacquers composed ofcellulose esters, cellulose ethers and vinyl derivatives, for example,also can be 001-.

ored. Coloration can be efiected b-y dyeing, printing, stenciling orother suitable methods.

It is an object of our invention to provide a new class of azo dyecompounds. Another object of our invention is to provide a process forthe coloration of organic derivative of cellulose, wool, silk, nylon andVinyon textile materials. A further object is to provide colored textilematerials which possess good fastness properties and which are readilydischarged. A specific object is to provide colored cellulose acetatetextile materials which have good fastness and dischargeabilityproperties. Other objects will hereinafter appear.

Typical organic derivatives of cellulose include the hydrolyzed as wellas the unhydrolyzed cellulose organic acid esters such as celluloseacetate, cellulose formate, cellulose propionate or cellulose butyrateand the hydrolyzed as well as the unhydrolyzed mixed organic acid estersof cellulose such as cellulose acetate-propionate, celluloseacetate-butyrate and the cellulose ethers such as methyl cellulose,ethyl cellulose or benzyl cellulose.

The dyeings obtained with the dye compounds of our invention arecharacterized by exceptional light fastness and by good fastnessproperties to gas fumes, washing and perspiration. Further, the dyecompounds of our invention possess good aflinity for the textilematerials named and can be applied rapidly thereto at relatively lowtemperatures. The advantages of the dye compounds appear to be realizedto their greatest extent when cellulose acetate is the material to becolored.

The azo compounds of our invention can be prepared by diazotizingcompounds having the wherein R has the meaning previously assigned to itand cdupling the diazonium compounds obtained with the compounds havingthe formula:

Example 1 (A) One gram mole of sodium nitrite is dissolved at 15 C. in530 cc. of 93% sulfuric acid,

.. the mixture heated to C. and then cooled to (B) One gram mole ofZ-amino-E-nitrophenylmethylsulfonamide is dissolved in 2200 cc. of hotacetic acid and rapidly cooled to 10-15 C.

The diazotization is carried out by adding, soluin accordance with theprocedure described in Example 1. The dye compound obtained colorscellulose acetate pinkish-rubine shades which are bluer than thoseobtained with the dye of tion B to solution A over a period of 30-45min- Example 2. The dyeings obtained possess excelutes, whilemaintaining a temperature of -15 lent light fastness properties. C. andstirring continuously. Upon completion of the diazotization reaction,the reaction mixture Example 4 is poured into water and the yellowdiazonium 1 gram mole of 2 amino 5 nitr0pheny1 p $0131 g g s 1S x byfiltratlon w methoxyethylsulfonamide is diazotized and the gi g g g g ig355m the diazonium diazonium compound obtained is coupled with 1 grammole of ethyl-,B,' -dihydroxypr0pyl-mg fifi ggg ig 323:? Z; fi s a; fi ggg toluidine. The diazotization and coupling reac- 0 0 g e y 2' y tionscan be carried out in accordance with the ethylamline. Throughout thecoupling reaction procedure described in Example 1 The dye Z P Ei i 3igig agfi g g figg pound obtained colors cellulose acetate pinkisht m if violet shades which possess excellent light fastti l rii r: 15153111which the l e com ness properties' g by filtration ywashed The followingtabulation further illustrates the 511th water and dr ed The y compdundob compounds included within the scope of our d which has f0rmmainvention together with the color they produce l OH on the textilematerials named herein. The com- 3 pounds indicated below may beprepared by di- N z-N=N -N\ azotizing the amines listed under theheading I I H v 011,011,011 Amine and coupling the diazom'um compoundsobtained with the compounds in the column H entitled Coupling component.The diazotize- CH8 tron and coupling reactions may, for example, becolors cellulose acetate pinkish-rubine shades. carried out followingthe general. procedure dewhich have splendid light fastness properties.scribed in Xamp eS 1 t inclusive- Am'ine Coupling component Color (1)zmino-5-nitrophenylmethylsulfonamide Methyl-Brhydroxycthylaniline 1.Pink. (2) 2-amin0-5-nitrophenylethylsulionamide 0 D0, (3)2-arnino-5-nitrophenylpropylsulfonamide Do. (4)2-aminc-5-nitrophenylbutylsulfonamide D0, (5)2-amino-5-nitrophenylallylsulfonamide Do. (6)2-amigo-5-nitrophenyl-fi-methoxyethylsulfon- D 81111 8. (7)2-arngno-5-nitropheny1-fi-ethoxyethylsulfona- D0,

1111 8'. (8), 2-alncilno-5-nitrophenyl-fl-hydroxyethylsulfona- 1)Q m1 9.(9) 2-amiro-5-nitrophonyl-B-hydroxypropylsulfon- D0.

am! 8. (10) 2-ami 1[11o'-5-nitrophenyl-'y-hydroxypropylsulfon- D0 8111!6. 1-10 above t yl-fl-hydroxypropylaniline D0, D0Allyl-fl-hydroxyethylaniline D0, Allyl-fi-hydroxypropylaniline D o.Allyl-B-methoxyethylaniline Do. B-Methoxyethyl-B,' -dihydroxypropylanine Do. Di-fi-methoxyethylaniline D o. BHydroxypropyl-y-hydroxypropylani1 ine 1 Do. M ethyl-5, 'y-dlhydroxypropyl-m-toluidine Pinkislrrubino.Methyl-fi-eth oxyethyl-m-toluidinc D o.Methyl-B-hydroxypropyl-m-toluidine Do. Ethyl-fl-hydroxyethyl-m-toluidinel D o. Ethyl- -hydroxypropyl-rn-toluidine 4. D0.B-Methoxyethyl-fi-hydroxyethyI-m-toluidine D o. fl-Ethoxyethyl-B-hydroxyethyl-m-toluidinc D o.B-Hydroxyethyl-B-hydroxypropyl-m-toluidinc. Do.-y-Hydroxypropyl-fi-methoxycthyl-m-toluidins. Do.Allyl-fi,'y-dihydroxypropyl-m-toluidine Do.Allyl-y-hydroxypropyl-m-toluidine Do.

Example 2 1 gram mole of 2-amino-5-nitrophenylethylsulfonamide isdiazotized and the diazonium compound obtained is coupled with 1 grammole of di-fi-hydroxyethylaniline. The diazotization and couplingreactions maybe carried out as described in Example 1. The dye compoundobtainedcolors cellulose acetate pinkish-rubine shades having excellentlight-fastness. properties.

Example 3 1 gram mole of 2-amino-5-nitrophenylethylsulfonamide isdiazotized and the diazonium compound obtained is coupled with 1 grammole of ethyl-fin dihydroxypropylaniline. The diazotization and couplingreactions can be carriedout 75. wherein R has the meaning previouslyassigned to it can be prepared as indicated by the following equations:

Chlorsulfonic acid O: C1 ll NOZQNHZ NOQOWHZ allyl halide I IS N AlkaliPrimary alkylamine N 02 O1 allylamine O: -01 O Any other suitablemethods can be employed.

In the first series of equations, it will be understood that the amountof alkylating or allylating agent used determines whether one or both ofthe hydrogen atoms of the sulfonamide groups is replaced by an alkyl orallyl group. In the present instance only suificient alkylating orallylating agent necessary to replace one hydrogen atom should be used.

2-amino-5-nitrophenylsulfonamide, 2-amino-5-nitrophenylmethylsulfonamide, 2-amino-5-nitrophenylethylsulfonamide andother similar type compounds can be prepared by the general methoddescribed by P. Fischer, Berichte der Deutschen Chemischen Gesellschaft,vol. 24, page 3790 (1891).

The coupling components used in the preparation of the azo dye compoundsof our invention can be prepared by methods known to those skilled inthe art. From the foregoing, the preparation of the components used inthe manufaoture of the azo dye compounds will be clear to those skilledin the art.

It is here noted that the term nylon refers to a linear polyamide resinwhich is believed to basically be described or claimed in U. S. LettersPatent 2,071,250, issued February 16, 1937, to Wallace H. Carothers. Theterm Vinyon refers to a vinyl chloride-vinyl acetate copolymer. Thismaterial is more completely identified at pages 73 and. 74 of SyntheticOrganic Chemicals, 10th edition, published October 15, 1940, by Carbide& Carbon Chemicals Corporation.

The azo compounds of our invention are, for the most part, relativelyinsoluble in water and,

accordingly, they may be advantageously directly (:5

applied to the material undergoing coloration in the form of an aqueoussuspension which can be prepared by grinding the dye to a paste in thepresence of a sulfonated oil, soap or other suitable dispersing agentand dispersing the resulting paste in water. In some instances, the dyemay possess sufficient solubility in water as to render the use of adispersing agent unnecessary. Generally speaking, however, the use of adispersing agent is desirable.

Direct dyeing operations can, with advantage, be conducted attemperatures of about 75-85 C. but any suitable temperature may be used.Thus, the textile material to be dyed or colored is ordinarily added tothe dyebath at a temperature lower than that at which the main portionof the dyeing is to be effected, a temperature approximating 45-55 C.,for example, following which the temperature is raised to that selectedfor carrying out the dyeing operation. The temperature at which thedyeing is conducted may, of course, be varied somewhat depending uponthe particular material undergoing coloration. As is understood by thoseskilled in the art, the intensity of dyeing can be varied by varying theproportion of dye to material undergoing coloration. Generally speaking,1'-3l% by weight of dye to material is employed although any desiredproportions can be used.

Suitable dispersing agents together with the amounts that may beemployed are disclosed in our Patent No. 2,115,030, issued April 26,1938. The process disclosed in this patent for the dyeing of celluloseacetate silk can be used in applying the dyes of the present applicationto this material.

It will be understood that the other textile 0 materials namedhereinbefore can be directly colored from an aqueous dyebath in asimilar manner as cellulose acetate silk. However, other suitablemethods for the dyeing of these materials are known to those skilled inthe art and these methods, of course, can be used in applying the dyecompounds of this application if desired. We would further note that,while colors yielded by the dye compounds have been given primarily withreference to cellulose acetate silk, generally similar colors areordinarily obtained on the other materials.

We claim;

1. The azo compound having the formula:

O=ISN (L 02H: 2. The azo compound having the formula:

' CnHs 3. The azo compounds having the general formula:

CHzCHgOH CH2OHOHOH2OH JAMES G. MCNALLY. JOSEPH B. DICKEY.

